CN1281855A - Preparation method of mixture of phenthiazine alkylate and diphenylamine - Google Patents

Preparation method of mixture of phenthiazine alkylate and diphenylamine Download PDF

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CN1281855A
CN1281855A CN00120445A CN00120445A CN1281855A CN 1281855 A CN1281855 A CN 1281855A CN 00120445 A CN00120445 A CN 00120445A CN 00120445 A CN00120445 A CN 00120445A CN 1281855 A CN1281855 A CN 1281855A
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mixture
pentanoic
alkyl
iii
hydrogen
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CN1156460C (en
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S·埃范斯
S·阿伦巴赫
P·杜布斯
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/36—[b, e]-condensed, at least one with a further condensed benzene ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/20—[b, e]-condensed with two six-membered rings with hydrogen atoms directly attached to the ring nitrogen atom

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Lubricants (AREA)

Abstract

This invention relates to a novel, technically advantageous process for the preparation of a mixture of alkylated phenothiazines and diphenylamines. Starting from diphenylamine, this is reacted with elemental sulfur in the presence of iodine, and the substance mixture of diphenylamine and phenothiazine is treated with an olefin in the presence of an acid catalyst.

Description

The preparation method of mixture of alkylated phenthazine and pentanoic
The present invention relates to a kind of novelty and the superior method for preparing alkylated phenthazine and diphenylamine compound on the technology.
The many organic productss that have extensive use on industrial technology in lubricant, hydraulic fluid, metal working fluid, fuel or polymkeric substance, often add additive, so that improve its serviceability.
When the liquid mixture of amine antioxidants has been used some, particularly be applied in the internal combustion (IC) engine lubricating oil.Prepare thiodiphenylamine from US-2433658 is known by pentanoic and reaction of Salmon-Saxl.EP-A-0 475 904 has narrated the mixture for preparing alkylated phenthazine by alkylated diphenylamine and reaction of Salmon-Saxl.Alkylated diphenylamine compound then is prepared in advance by EP-A-0 149 422 described methods, this method comprise make pentanoic with as the alkene of alkylating agent, react as diisobutylene.Alkylation process is not very selectively because what obtain is the mixture of different alkylates, for example 2,2 '-, 2,4 '-, 4-, 4,4 '-and 2,4, the mixture of 4 '-alkylated diphenylamine.This class mixture reacts according to EP-A-0 475 904 described methods subsequently, makes the mixture of corresponding alkylated diphenylamine and thiodiphenylamine with low selectivity.
General purpose of the present invention provides 3-and the alkylated diphenylamine of 7-position alkylated reaction selectivity raising and the mixture of thiodiphenylamine.
EP-A-0 659 749 has narrated to adopt and has made the mixture of pentanoic and thiodiphenylamine carry out selective alkylation reaction such as alkene such as diisobutylene.Yet this method disadvantage is that the described synthetic mixture of pentanoic and thiodiphenylamine that requires needs to exist as starting material.
Purpose of the present invention more clearly is defined in: from pure pentanoic of only starting material or naphthylamines, and the alkylated diphenylamine that preparation 3-and 7-position alkylation selectivity improve and the mixture of thiodiphenylamine.
Realize this purpose by the preparation alkylated phenthazine that the present invention relates to and so-called single still method of diphenylamine compound.
The present invention relates to prepare the method for the diphenylamine compound that comprises logical formula I alkylated phenthazine and the corresponding replacement of logical formula II;
Figure 0012044500061
In the formula, R 1And R 2Be hydrogen, perhaps connecting together is following radicals (A)
Figure 0012044500062
R 3And R 3 'One of be hydrogen, another is C 2～C 30Alkyl, ring C 5～C 12Alkyl-C 2～C 4Alkyl, α-C 1～C 2Alkyl benzyl or α, α-Er Jiajibianji; Perhaps, if R 1And R 2Be hydrogen, R so 3And R 3 'Both are C 2～C 30Alkyl, ring-C 5～C 12Alkyl-C 2～C 4Alkyl, α-C 1～C 2Alkyl benzyl or α, α-Er Jiajibianji; If perhaps R 1And R 2Connect together is group A, R so 3Be hydrogen and R 3 'Be C 2～C 30Alkyl, ring-C 5～C 12Alkyl-C 2～C 4Alkyl, α-C 1～C 2Alkyl benzyl or α, α-Er Jiajibianji; Described method comprises: in the presence of the condensation catalyst that is selected from iodine, aluminum bromide, aluminum chloride, iron(ic) chloride (III), antimony chloride, cupric iodide and sulfur iodide, general formula III pentanoic and elementary sulfur are reacted:
Figure 0012044500063
In the formula, R 1And R 2Define as formula I; And in the presence of acid catalyst, the pentanoic (III) of gained and the mixture of logical formula IV thiodiphenylamine are reacted on the spot with general formula (V) alkene,
Figure 0012044500071
R in the formula 1And R 2Define as formula I, This formula contains R 3Or R 3 'In the carbon atom number, R wherein 3 a, R 3 bAnd R 3 cOne of be the ring C 5～C 12Alkyl or phenyl, and other group is hydrogen or methyl, perhaps R 3 a, R 3 bAnd R 3 cEach hydrogen or C naturally each other have nothing to do 1～C 28Alkyl; The mixture of compound (I) and (II) of emanating out then.
In particularly preferred embodiment of the present invention, two processing steps are finished with a still.
Be defined as C 2～C 30The R of alkyl 3And R 3' be preferably C 2～C 20Alkyl, more preferably C 4～C 12Alkyl, side chain or side chain (from 3 carbon atoms) alkyl for example, be generally ethyl, just-propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, just-hexyl, 2-ethyl-normal-butyl, 1-methyl-n-pentyl, 1, the 3-dimethylbutyl, n-heptyl, different heptyl, 1,1,3, the 3-tetramethyl butyl, 1-methyl hexyl, 2-methyl hexyl, n-octyl, iso-octyl, 1,4,4-trimethylammonium-2-amyl group, the 1-methylheptane, just-nonyl, 1,1,3-trimethylammonium hexyl, positive decyl, the n-undecane base, dodecyl, 1-methyl undecyl, dodecyl, the n-tetradecane base, n-hexadecyl, Octadecane base or NSC 62789 base.
Ring C 5～C 12Alkyl-C 2～C 4Alkyl for example is a cyclopentyl-1,1-ethyl, cyclohexyl-1,1-ethyl, cyclopentyl-1,2-ethyl, cyclohexyl-1,2-ethyl, cyclopentyl-1,2-propyl group or cyclohexyl-1,2-propyl group.
α-C 1～C 2Alkyl benzyl for example is methyl-benzyl (=1, the 1-styroyl).
In the preferred embodiment of present method, be reflected at about 0.001～10mol% condensation catalyst and exist down, adopt about 0.5～200mol% elementary sulfur, under about 80～250 ℃, carry out.Described condensation catalyst is selected from iodine, aluminum bromide, aluminum chloride, iron(ic) chloride (III), antimony chloride, cupric iodide and sulfur iodide.
In another preferred embodiment of present method, 10～150mol% elementary sulfur is adopted in reaction, is preferably 15～100mol%.
The preferred embodiment of present method comprises that employing 0.001～1.0mol% condensation catalyst reacts.
In present method particularly preferred embodiment, reaction adopts 0.001～0.01mol% elemental iodine to carry out.
Temperature of reaction is about 80 ℃～250 ℃, is preferably 120 ℃～190 ℃.In the reaction process, form hydrogen sulfide (H 2S).Because the toxicity and the niff of hydrogen sulfide so it is discharged from reaction vessel, import in the alkali metal hydroxide aqueous solution.Form alkali-metal sulfide, can easily dispose later on.
In first processing step, the reaction times is for example about 1～15hr.Reaction times, 2～4hr used always, preferred about 1～2hr.
Reaction can be by being added in sulphur and the catalyzer and carrying out suitably being dissolved in pentanoic (III) in one of cited solvent.Heating gained mixture stirs, simultaneously to described humidity.Can observe reaction process by hydrogen sulfide formation.After the described reaction times, perhaps to analyze when showing without any free sulphur, the reaction of first processing step can finish, and for example, reaction vessel is cooled to about 100 ℃ of termination reactions.
Compound (III) and (IV) mixture with mol ratio about 95: 5 to 5: 95 can be preferably 30: 70 to 70: 30 and be applied in second processing step.
In selection process second processing step of present method, the mol ratio of employed compound (III) and compound (IV) is about 30: 70 to 5: 95, preferred especially 20: 80 to 10: 90.
In second processing step, use alkene (V), in the mixture of every mole compound (III) and (IV), this alkene mole number is about 0.5～4.0mol, is preferably 1.0～3.0mol, more preferably 1.0～2.0mol.
Carbonatoms in the alkene (V) is equivalent to R 3Or R 3 'In carbonatoms.If R 3Or R 3 'Be uncle's octyl group or 1,4,4-trimethylammonium-2-amyl group uses diisobutylene to make alkene (V) so.Other suitable alkene for example is ethene, propylene, iso-butylene, 2-methyl-amylene, tripropylene, tetrapropylene, vinylbenzene or vinyl toluene.
Suitable acid catalyst is proton donor (so-called Bronsted acid), electron acceptor compound (so-called Lewis acid), Zeo-karb, silico-aluminate or natural or modified sheeted silicate.
Suitable proton donor (so-called Bronsted acid) for example is salifiable inorganic or organic acid, for example, and mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid, carboxylic acids such as acetate, perhaps sulfonic acid such as methylsulfonic acid, Phenylsulfonic acid or tosic acid.Tosic acid is suitable especially.
Suitable electron acceptor compound (so-called Lewis acid) for example is tin tetrachloride, zinc chloride, aluminum chloride or boron trifluoride etherate.Tin tetrachloride and aluminum chloride are suitable especially.
Suitable Zeo-karb for example is the styrene diethylene benzene copoly mer that has contained the sulfonic acid group of ion exchange, as the known product Amberlite of Rohm and Hass company And Amberlyst , as AMBERLiTE200, the perhaps Dowex of Dow Chemicals company 50, perfluoro ion exchange resin is as the Nafion of DuPont company H, perhaps other super acids ion exchange resin, as T.Yamaguchi at " applied catalysis " (Applied Catalysis) 61, in 1～25 (1990), perhaps M.Hino etc. in " chemistry can will chemistry circular " (J.Chem.Soc.Chemical Comm) 1980,851～852, narrated those.
Suitable silico-aluminate, for example be contain have an appointment 10～30% silicon-dioxide and about 70～90% aluminum oxide, be used in the amorphous aluminum silicate in the petroleum chemistry, as the Aluminium Silicate HA-HPV of Ketjen (AKzo) , or crystalline aluminosilicate, as being used as inorganic cation exchange agent, being called molecular sieve, perhaps in petroleum chemistry, be called the so-called zeolite of cracking catalyst, as the faujusite of Union Carbide company, as Zeolith R , Zeolith Y With overstable zeolite; The Zeolith Beta of Mobil Oil company With Zeolith ZSM-12 , the perhaps Zeolith Mordenit of Norton company
Suitable natural sheet silicate is also referred to as sour soil, be to use as mineral acid activatory, preferred water content such as sulfuric acid and/or hydrochloric acid below 10%, the more preferably polynite below 5%, for example, so-called Fuller type soil is as the commodity of Laporte Industries company Fulcat by name Commercially available type as 20,22A, 22B and 40 types (sulfuric acid activatory aluminum oxide), trade(brand)name Fulmont As XMP-4, XMP-3,700C and 237, the perhaps sour soil of the model K0 of S ü dchemie company and K10 (using hydrochloric acid activation), KS and KSF (activating with sulfuric acid) or KSFO (with the activation of hydrochloric acid and sulfuric acid), and based on the soil of wilkinite is Filtrol as the model of Engelhard company Or Retrol Product.
The particularly preferred embodiment of the inventive method comprises the polynite of using Fulcat  22B and acid activation, and the latter is contained 4% free-water, and the acidometric titration degree is 20mg KOH/g.
Modified sheeted silicate is also referred to as pillared clays, and it contains oxide compound or rare earth element such as zirconium, iron, zinc, nickel, chromium, cobalt or magnesium derived from above-mentioned natural sheet silicate between this silicate layer.The sheet silicate of modification, especially by people such as J.Clark at " chemistry can will chemistry circular ", introduced in 1989,1353～1354.Particularly preferred modified sheeted silicate for example is the product E nvirocat that Contract Chemicals company produces EPZ-10, EPZG or EPIC.
An acidic catalyst can following dosage adds, 1～50wt% for example, preferred 5～25wt%, preferred especially 5～20wt%, perhaps, if so-called Bronsted acid or Lewis acid, consumption is 0.002～10mol% so, is preferably 0.1～5.0mol%.
Temperature of reaction in second reactions steps is about 60～250 ℃, is preferably 110～200 ℃, is preferably 160～195 ℃ especially.
In two reactions steps, reaction can be carried out under employing (perhaps preferably not adopting) solvent or thinner.If the use solvent, solvent should be inert under given reaction conditions so, and suitably high boiling point should be arranged.The suitable solvent for example is halohydrocarbon, polar aprotic solvent, liquid amide and the alcohol that optionally adopts.Can mention sherwood oil cut (preferred high boiling point person) as row, toluene,, dichlorobenzene, tetrahydrofuran (THF) (THF), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), hexamethyl phosphoric triamide (HMPTA), glyme, diglyme, dimethyl sulfoxide (DMSO) (DMSO), tetramethyl-urea (TMU), alcohols, as butanols or ethylene glycol.
The order of processing step can illustrate as follows, for example: by react the mixture of preparation alkylated diphenylamine and thiodiphenylamine with diisobutylene:
Figure 0012044500111
The present invention preferably relates to the method for preparing alkylated phenthazine (I) and pentanoic (II) mixture, this method comprises: in the presence of the condensation catalyst that is selected from iodine, aluminum bromide, aluminum chloride, iron(ic) chloride (III), antimony chloride, cupric iodide and sulfur iodide, pentanoic (III) and elementary sulfur are reacted; The pentanoic (III) of gained and the mixture of thiodiphenylamine (IV) are reacted with alkene (V) on the spot, and alkene (V) contains R3 or R 3 'In the carbon atom number, R wherein 3 a, R 3 bAnd R 3 cDefinition as described above; The mixture of compound (I) and (II) of emanating out then.
The present invention especially preferably relates to the method for the mixture of preparation alkylated phenthazine (I) and pentanoic (II), and this method comprises: in the presence of the iodine as condensation catalyst, pentanoic (III) and elementary sulfur are reacted; The pentanoic (III) of gained and the mixture of thiodiphenylamine (IV) are reacted with alkene (V) on the spot, and alkene (V) contains R 3Or R 3 'In the carbon atom number, R wherein 3 a, R 3 bAnd R 3 cDefinition as described above; The mixture of compound (I) and (II) of emanating out then.
Another embodiment preferred relates to the method for the mixture of preparation alkylated phenthazine (I) and pentanoic (II), wherein R 1And R 2Be hydrogen, R 3And R 3 'One of be hydrogen, and another is 1,4,4-trimethylammonium-2-amyl group or nonyl, perhaps R 3And R 3 'Both are 1,4,4-trimethylammonium-2-amyl group or nonyl; This method comprises: in the presence of the iodine as condensation catalyst, make pentanoic (III), wherein R 1And R 2Be hydrogen, react with elementary sulfur; In the presence of acid catalyst, the mixture of prepared pentanoic (III) and thiodiphenylamine (IV) is reacted on the spot with diisobutylene or tripropylene; The mixture of compound (I) and (II) of emanating out then.
The alkylated phenthazine (I) that makes according to method of the present invention and the mixture of pentanoic (II) are applicable to stablizes the anti-light of organic compound, heat and/or oxidative degradation.These mixtures especially can be used as stablizer and following suitable substrate combination is used, described matrix can be synthetic, semi-synthetic or natural polymer, particularly thermoplastics and elastomerics also have functional fluid, particularly lubricant, metal working fluid and hydraulic fluid.
Listed functional fluid, for example lubricating composition lubricating grease, gear oil, metal-working fluids and hydraulic fluid etc. also can contain other additive, so that further improve its fundamental property.These additives comprise: antioxidant, metal passivator, rust-preventive agent, viscosity index improver, stagnation point (stock point) inhibitor, dispersion agent, washing agent, high pressure additive and anti-wear agent.The common add-on of these additives about 0.01～10.0wt% that respectively does for oneself respectively.
Cited component can known method own be sneaked in the lubricant.Also can prepare concentrated solution or so-called additive blends, can be diluted to the used concentration of associated lubrication agent according to consumption.
Inorganic and the ucon oil of improvement like this, lubricating grease, hydraulic fluid and elastomerics have good antioxygen property, show as its material ageing resistance of protecting and significantly improve.These mixtures are particularly advantageous in lubricating oil, show as antioxygen and anticorrosive effect is good, and do not form any acid or residue.
Mix or apply the mixture that the inventive method makes and the additive of adding optionally with conventional process, can be incorporated in the material of various Application Areass.
Now with following example explanation the present invention.
Example 1
1.1 507.7g (3.0mol) pentanoic and 26.75g (0.834mol) sulphur are placed the oil bath that is heated to 195 ℃.Under the temperature, add 0.1g (0.0016mol) iodine in about 100 ℃, temperature further raises.After reaction times 15min, temperature reaches 175 ℃, and at this moment, hydrogen sulfide begins to isolate, and is decomposed by it being imported 5% aqueous sodium hydroxide solution.Temperature constant temperature is controlled 45min at 185 ℃.Thin-layer chromatographic analysis (DC) shows, is detected without any sulphur in the browning reaction mixture.
1.2. the material of processing step 1.1. is cooled to about 100 ℃.Add 132g (1.176mol) diisobutylene and 50g FULCAT 22B, reheat material by the gross until vigorous reflux, and is isolated about 9ml water in water separator.Behind reaction times 30min, interior temperature rise to 184 ℃.Drip the other diisobutylene of 396.5g (3.534mol), its speed will make temperature not be reduced to below 165 ℃ that (the dropping time is 5 1 2 hr )。(170～175 ℃) made mixture reaction 2 hours under constant temperature then, finished until reaction.
1.3. with gained by the gross material be cooled to about 50 ℃, then with the dilution of 400ml hexane.Remove by filter catalyzer, in rotatory evaporator, concentrate light yellow filtrate.10 -2Under the mbar vacuum,,, from light yellow oil, distill out unreacted pentanoic with 3hr in bathing under warm 150 ℃.Make the transparent oily matter of 867.3g light tan.
Characterized
Ultimate analysis: 4.25%N, 1.29%S.Mixture is through gas chromatographic analysis, and its composition sees the following form.
Example 2
Can prepare the higher mixture of thiodiphenylamine content by adding relatively large sulphur.Step is similar to example 1, only is to use 48.1g (1.5mol) sulphur.Make the transparent oily matter of 893g light tan.
Characterized
Ultimate analysis: 4.38%N, 2.75%S.Mixture is through gas chromatographic analysis, and its composition sees the following form.
Example 3
By adding relatively large sulphur, use relatively large diisobutylene to carry out alkylation, can prepare the mixture that thiodiphenylamine content is higher, the alkylation degree is higher.Step is similar to example 1, only is to use 144.3g (4.5mol) sulphur, 158g diisobutylene.Make the transparent oily matter of 928g light tan.
Characterized
Ultimate analysis: 4.19%N, 7.07%S.Mixture is through gas chromatographic analysis, and its composition sees the following form.
Table: according to the mixture group of gas chromatographic analysis
Figure 0012044500141
Figure 0012044500142
1) gas chromatograph: HP 5890,2 types; Post: Macherey-Nagel, Optima-5 amine, 30 * 0.32,1 μ m.2) distill out after the pentanoic
Example 4
4.1. 338.45g (2.0mol) pentanoic and 96.2g (3mol) sulphur are placed the oil bath that is heated to 195 ℃.Under about 100 ℃ of interior temperature, add 0.1g (0.0016mol) iodine, temperature is further raise.Behind reaction times 40min, temperature reaches 175 ℃, and begin to isolate hydrogen sulfide this moment, is decomposed by it being imported 5% aqueous sodium hydroxide solution.Make temperature constant temperature under 185 ℃, control 45min.
4.2. the material by the gross that processing step 1.1 is obtained is cooled to about 100 ℃.Add 250g tripropylene (nonene) and 35g FULCAT 22B, reheat gained material in water separator until vigorous reflux, is isolated about 9ml water.Behind reaction times 30min, interior temperature rise to 164 ℃.Subsequently, drip the 760g tripropylene with 3hr.Temperature is reduced to 143 ℃.Then, (143 ℃～145 ℃) finish reaction through 6hr under constant temperature.
4.3. with gained by the gross material be cooled to about 50 ℃, then with the dilution of 400ml hexane.Remove by filter catalyzer, in rotatory evaporator, concentrate light yellow filtrate.In rotatory evaporator, from light yellow filtrate, remove the tripropylene that does not have reaction.Brown oil is 10 -2Mbar and bathing under 80 ℃ of the temperature through the 3hr drying makes the transparent oily matter of 721.6g brown.
Characterized
Ultimate analysis: 4.28%N, 6.56%S.

Claims (6)

1. one kind prepares the method that comprises the diphenylamine compound that leads to formula I alkylated phenthazine and the corresponding replacement of logical formula II;
Figure 0012044500021
In the formula, R 1And R 2Be hydrogen, perhaps connecting together is following radicals (A)
Figure 0012044500022
R 3And R 3 'One of be hydrogen, another is C 2～C 30Alkyl, ring C 5～C 12Alkyl-C 2～C 4Alkyl, α-C 1～C 2Alkyl benzyl or α, α-Er Jiajibianji; Perhaps, if R 1And R 2Be hydrogen, R so 3And R3 ' both are C 2～C 30Alkyl, ring-C 5～C 12Alkyl-C 2～C 4Alkyl, α-C 1～C 2Alkyl benzyl or α, α-Er Jiajibianji; If perhaps R 1And R 2Connect together is group A, R so 3Be hydrogen and R 3 'Be C 2～C 30Alkyl, ring-C 5～C 12Alkyl-C 2～C 4Alkyl, α-C 1～C 2Alkyl benzyl or α, α-Er Jiajibianji; Described method comprises: in the presence of the condensation catalyst that is selected from iodine, aluminum bromide, aluminum chloride, iron(ic) chloride (III), antimony chloride, cupric iodide and sulfur iodide, general formula III pentanoic and elementary sulfur are reacted: In the formula, R 1And R 2Define as formula I; And in the presence of acid catalyst, the pentanoic (III) of gained and the mixture of logical formula IV thiodiphenylamine are reacted on the spot with general formula (V) alkene, R in the formula 1And R 2Define as formula I, This formula contains R 3Or R 3 'In the carbon atom number, R wherein 3 a, R 3 bAnd R 3 cOne of be the ring C 5～C 12Alkyl or phenyl, and other group is hydrogen or methyl, perhaps R 3 a, R 3 bAnd R 3 cEach hydrogen or C naturally each other have nothing to do 1～C 28Alkyl; The mixture of compound (I) and (II) of emanating out then.
2. according to the method for preparing alkylated phenthazine (I) and pentanoic (II) mixture of claim 1, this method comprises: in the presence of the condensation catalyst that is selected from iodine, aluminum bromide, aluminum chloride, iron(ic) chloride (III), antimony chloride, cupric iodide and sulfur iodide, pentanoic (III) and elementary sulfur are reacted; The pentanoic (III) of gained and the mixture of thiodiphenylamine (IV) are reacted with alkene (V) on the spot, and alkene (V) contains R 3Or R 3 'In the carbon atom number, R wherein 3 a, R 3 bAnd R 3 cDefinition as described above; The mixture of compound (I) and (II) of emanating out then.
3. according to the method for the mixture of the preparation alkylated phenthazine (I) of claim 1 and pentanoic (II), this method comprises: in the presence of the iodine as condensation catalyst, pentanoic (III) and elementary sulfur are reacted; The pentanoic (III) of gained and the mixture of thiodiphenylamine (IV) are reacted with alkene (V) on the spot, and alkene (V) contains R 3Or R 3 'In the carbon atom number, R wherein 3 a, R 3 bAnd R 3 cDefinition as described above; The mixture of compound (I) and (II) of emanating out then.
4. according to the method for the mixture of the preparation alkylated phenthazine (I) of claim 1 and pentanoic (II), R wherein 1And R 2Be hydrogen, R 3And R 3 'One of be hydrogen, and another is 1,4,4-trimethylammonium-2-amyl group or nonyl, perhaps R 3And R 3 'Both are 1,4,4-trimethylammonium-2-amyl group or nonyl; This method comprises: in the presence of the iodine as condensation catalyst, make pentanoic (III), wherein R 1And R 2Be hydrogen, react with elementary sulfur; In the presence of acid catalyst, the mixture of prepared pentanoic (III) and thiodiphenylamine (IV) is reacted on the spot with diisobutylene or tripropylene; The mixture of compound (I) and (II) of emanating out then.
5. according to the method for the mixture of the preparation alkylated phenthazine (I) of claim 1 and pentanoic (II), R wherein 1And R 2Be hydrogen, R 3And R 3 'One of be hydrogen, and another is 1,4,4-trimethylammonium-2-amyl group or nonyl, perhaps R 3And R 3 'Both are 1,4,4-trimethylammonium-2-amyl group or nonyl; This method comprises: in the presence of the iodine as condensation catalyst, make pentanoic (III), wherein R 1And R 2Be hydrogen, react with elementary sulfur; With sheet silicate, polynite is that the active catalyst on basis exists down, perhaps in the presence of wilkinite be basic soil, the mixture of prepared pentanoic (III) and thiodiphenylamine (IV) is reacted on the spot with diisobutylene or tripropylene; The mixture of compound (I) and (II) of emanating out then.
6. according to the method for the mixture of the preparation alkylated phenthazine (I) of claim 1 and pentanoic (II), this method comprises to be finished two processing steps with a still technology.
CNB001204459A 1999-07-09 2000-07-07 Preparation method of mixture of phenthiazine alkylate and diphenylamine Expired - Fee Related CN1156460C (en)

Applications Claiming Priority (2)

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CH128099 1999-07-09
CH1280/1999 1999-07-09

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CN1281855A true CN1281855A (en) 2001-01-31
CN1156460C CN1156460C (en) 2004-07-07

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CN116060101A (en) * 2021-10-31 2023-05-05 中国石油化工股份有限公司 Catalyst for synthesizing diphenylamine, preparation method and application thereof

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US7176168B2 (en) * 2003-03-28 2007-02-13 Exxonmobil Research And Engineering Company Lubricant containing a synergistic combination of rust inhibitors, antiwear agents, and a phenothiazine antioxidant
EP2998303B1 (en) 2014-09-17 2018-06-13 B & G Partners, LLC Phenothiazine derivatives and methods for treating tumors
US20170009174A1 (en) * 2015-07-07 2017-01-12 Exxonmobil Research And Engineering Company Multifunctional lubricating oil base stocks and processes for preparing same
CN116425637A (en) * 2022-01-01 2023-07-14 中国石油化工股份有限公司 Method and device for preparing diphenylamine and phenothiazine from aniline

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN101082010B (en) * 2006-05-31 2010-10-27 中国石油化工股份有限公司 Liquid alkylated phenthazine and diphenylamine mixture and preparation method and application thereof
CN116060101A (en) * 2021-10-31 2023-05-05 中国石油化工股份有限公司 Catalyst for synthesizing diphenylamine, preparation method and application thereof

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JP2001072649A (en) 2001-03-21
KR20010066912A (en) 2001-07-11
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EP1067124A1 (en) 2001-01-10
CN1156460C (en) 2004-07-07
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SK10422000A3 (en) 2001-02-12

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